CN108373158A - Compound fluoboric acid beryllium and fluoboric acid beryllium nonlinear optical crystal and its preparation method and application - Google Patents

Compound fluoboric acid beryllium and fluoboric acid beryllium nonlinear optical crystal and its preparation method and application Download PDF

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CN108373158A
CN108373158A CN201810239405.9A CN201810239405A CN108373158A CN 108373158 A CN108373158 A CN 108373158A CN 201810239405 A CN201810239405 A CN 201810239405A CN 108373158 A CN108373158 A CN 108373158A
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crystal
compound
quartz ampoule
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潘世烈
卞强
杨志华
侯雪玲
韩健
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Xinjiang Technical Institute of Physics and Chemistry of CAS
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    • H01S3/108—Controlling the intensity, frequency, phase, polarisation or direction of the emitted radiation, e.g. switching, gating, modulating or demodulating by controlling devices placed within the cavity using non-linear optical devices, e.g. exhibiting Brillouin or Raman scattering
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Abstract

The present invention relates to a kind of compound fluoboric acid beryllium and fluoboric acid beryllium nonlinear optical crystal and its preparation method and application, the chemical formula of the compound is Be2(BO3) F, molecular weight 95.83, using hydro-thermal method or solid reaction process synthesis compound, the molecular formula of the crystal is Be2(BO3) F, molecular weight 95.83 belongs to hexagonal crystal system, and space group isCell parameter is α=β=90 °, γ=120 °, Z=2,It is prepared using hydro-thermal method or high temperature solution method, nonlinear optical effect is about KDP (KH2PO4) 1.8 times, there is higher transmitance in the range of 7 μm of 200nm, it is 138nm that UV transmission, which ends side, and infrared through cut-off side is 8.5 μm.The crystal growing process has the advantages that easy to operate, at low cost, growth cycle is short, and physico-chemical property is stablized.It can be used widely in the device for non-linear optical such as frequency-doubled conversion, optical parametric oscillator.

Description

Compound fluoboric acid beryllium and fluoboric acid beryllium nonlinear optical crystal and preparation method thereof and Purposes
Technical field
The present invention relates to a kind of compound fluoboric acid beryllium and fluoboric acid beryllium nonlinear optical crystal and preparation method thereof and use On the way, belong to domain of inorganic chemistry, also belong to crystallography field, materials science field and optical field.
Background technology
Nineteen sixty T.M.Maiman has studied successfully First ruby (Cr in the world3+:Al2O3) pulse laser, from Since this laser became for 20th century, after atomic energy, computer, semiconductor, the another very great invention of the mankind, and Scientific research, industry, traffic, national defence and health care etc. play an increasingly important role.But currently various lasers are straight The laser wavelength for connecing output is limited, and laser blank wave band has been remained from ultraviolet band to infrared band.With current tunable range Maximum Ti∶Sapphire laser (Ti:Al2O3) for laser, maximum tunable range is only between 670nm-1100nm, far from full Sufficient Development of Laser Technology needs.P.A.Franken in 1961 is by ruby laser incidence crystal (α-SiO2), it is found that crystalline substance for the first time Frequency-doubled effect caused by body.Hereafter, nonlinear optical crystal is studied to obtain development at full speed, utilizes non-linear optical crystal Body widens laser radiation wavelength range, becomes the important means for opening up new laser light source.
Borate nonlinear optical crystal is the most wide laser frequency crystal of current application, therefore is visited in borate salt system Rope Novel variable-frequency crystal simultaneously realizes that the high efficiency of optical maser wavelength is converted into the hot spot that laser field is paid close attention to always.Especially in essence Ultraviolet and deep ultraviolet laser coherent source is had increasing need in the development in the fields such as close micro Process, laser ablation, photo-optics, i.e., Need the ultraviolet and deep ultraviolet nonlinear optical crystal haveing excellent performance.The ultraviolet nonlinear crystal of widely applied borate in the world Material mainly has barium metaborate (β-BaB2O4, β-BBO) and three lithium borate (LiB3O5, LBO), this be Chinese Scientists respectively at It invents within 1985 and 1989.Chinese Academy of Sciences's nineties in last century Fujian object structure successfully has developed KBe2(BO3)F2(KBBF) deep Ultraviolet nonlinear optical crystal, the crystal are the currently the only double-frequency materials that can realize the output of 177.3nm wavelength.KBBF group crystals It is China in nonlinear optical crystal research field, the 3rd China card non-linear optical crystal after finding BBO, lbo crystal Body has ground-breaking effect to the development and application that push all-solid-state deep ultraviolet laser source, also fully proves China non-thread Property optical crystal field continue keep the leading level in the world.1978, I.A.Baidina et al. obtained space using hydro-thermal method Group is the Be of C22(BO3) F crystal, belong to monoclinic system, cell parameter a=0.7687nm, b=0.4439nm, c= 0.8699nm, β=107.08 °.2005, Xia Wenbing et al. tested its powder times using the solid state reaction kinetics compound Frequency is the 1/4 of KDP, and has carried out theoretical calculation to it.2015, peaceful et al. the application of the leaf of Fujian structure of matter research institute " nonlinear optical crystal fluoboric acid beryllium and its preparation method and application ", the Be reported in the patent2BO3F crystal structures belong to three Prismatic crystal system, space group R32, cell parameter areα=β= 90 °, γ=120 °, Z=3,Clock Multiplier Factor is about 2.2 times of KDP, and ultraviolet absorption edge is shorter than 180nm. 2016, Shu Guo et al. reported the Be of a centrosymmetric structure2BO3F crystal, and its structure and performance are ground Study carefully, crystal structure isSpace group, cell parameter areZ=2, but the crystal There is no frequency-doubled effect, cannot act as nonlinear optical crystal.
Nevertheless, the above crystal still deposits various shortcomings, high performance novel non-linearity light is being explored The important topic that crystalline material is photoelectric functional material field is learned, people are still preferably non-thread in the hope of discovery performance in continuous exploration Property optical crystal.In the ultraviolet nonlinear optical crystal of Development of Novel, still select transparency range wide, laser damage threshold is big Borate crystal, and in order to further widen transparency range, so that its ultraviolet cut-on side is reached deep ultraviolet, cation is usually Using the alkali or alkaline earth metal of no d-d electron transitions, and fluorine ion is introduced in borate skeleton.
Invention content
The object of the present invention is to provide a kind of compound fluoboric acid beryllium, the chemical formula of the compound is Be2(BO3) F, point Son amount 95.83 synthesizes compound using hydro-thermal method or solid reaction process.
Another object of the present invention is, provides that a kind of ultraviolet absorption edge is relatively low, and transmission region is wider, is easy to prepare and stablize Property preferable fluoboric acid beryllium nonlinear optical crystal, which is Be2(BO3) F, molecular weight 95.83, do not have pair Title center, belongs to hexagonal crystal system, and space group isCell parameter is α=β=90 °, γ=120 °, Z=2,
Still a further object of the present invention is, provides hydro-thermal method synthesis compound and growth crystal or solid reaction process synthesisization The method for closing object and high temperature solution method growth fluoboric acid beryllium nonlinear optical crystal.
Another object of the present invention is, provides a kind of purposes of fluoboric acid beryllium nonlinear optical crystal.
The chemical formula of a kind of compound fluoboric acid beryllium of the present invention, the compound is Be2(BO3) F, molecular weight is 95.83, compound is synthesized using hydro-thermal method or solid reaction process.
The chemical formula of a kind of fluoboric acid beryllium nonlinear optical crystal, the crystal is Be2(BO3) F, molecular weight 95.83, no With symmetrical centre, belong to hexagonal crystal system, space group isCell parameter is α=β=90 °, γ=120 °, Z=2,
The preparation method of the compound fluoboric acid beryllium nonlinear optical crystal synthesizes compound and growth using hydro-thermal method Crystal or solid reaction process synthesis compound and high temperature solution method grow crystal, and concrete operations follow these steps to carry out：
The hydro-thermal method synthesis compound and growth crystal：
A, Be in molar ratio:F:B=1-4:0.5-4:0.5-2 will contain Be compounds BeO, Be (OH)2、Be(NO3)2Or BeCO3It is dissolved in HF or HBF4In, B is then added2O3, by ultrasound of the mixture of endless fully dissolved in the case where temperature is 30-60 DEG C It is handled 1 hour in wave, it is made to be sufficiently mixed dissolving；
B, the solution in step a is transferred to poly- the four of clean, the free of contamination autoclave that volume is 25-100mL In vinyl fluoride liner, and by reaction kettle screwing hermetic；
C, the autoclave in step b is placed in insulating box, 150-230 is warming up to by the rate of 20-60 DEG C/h DEG C, constant temperature 3-15 days, then room temperature is down to 10-100 DEG C/day of rate of temperature fall, autoclave is opened, that is, obtains Be2(BO3)F Compound and seed crystal；
D, the Be that will be obtained in step c2(BO3) F seed crystals be put into volume be 25-100mL stainless steel autoclave platinum In golden liner, the Be obtained in step c is added2(BO3) F compounds, 1-15mL deionized waters are then added, and reaction kettle is revolved Autoclave is placed in Muffle furnace by tightening seal, is warming up to 250-500 DEG C by the rate of 20-60 DEG C/h, constant temperature 3-15 It, then room temperature is down to 10-100 DEG C/day of rate of temperature fall, autoclave is opened, that is, obtains Centimeter Level Be2(BO3) F is non-thread Property optical crystal；
The solid reaction process synthesis compound and high temperature solution method grow crystal：
A, Be compounds BeO, Be (OH) will be contained2、Be(NO3)2Or BeCO3, boride alloy H3BO3And B2O3, compound containing F For NH4F Be in molar ratio:F:B=1-4:0.5-4:0.5-2 is uniformly mixed, and is fitted into quartz ampoule and is sealed, is put into resistance furnace, It is warming up to 400-750 DEG C with the rate of 10-25 DEG C/h, then constant temperature 12-48 hours is down to 25 DEG C with the rate of 1-10 DEG C/h, Obtain compound Be2(BO3)F；
B, the compound Be for obtaining step a2(BO3) F is fitted into the quartz ampoule of Φ 10mm, quartz ampoule is vacuumized, vacuum Degree reaches 1 × 10-3Pa is put into flame gun Vacuum Package in Muffle furnace, and 400-750 is warming up to the rate of 10-25 DEG C/h DEG C, then constant temperature 12-60 hours is down to 25 DEG C with the rate of 1-5 DEG C/h, open quartz ampoule, obtain Be2(BO3) F seed crystal；
C, the Be for obtaining step b2(BO3) F seed crystals are placed on the bottom of clean, free of contamination quartz ampoule, then by step a Obtained compound Be2(BO3) F and fluxing agent be LiF, NaF, KF, LiF-B2O3、NaF-B2O3、KF-B2O3、H3BO3Or B2O3It presses Molar ratio 1:1-5 is mixed, and is put into quartz ampoule, quartz ampoule is vacuumized, vacuum degree reaches 1 × 10-3Pa, with flame gun vacuum seal Dress；
D, the container in step c is sealed, is put into resistance furnace, 400-750 DEG C is warming up to the rate of 20-40 DEG C/h, Constant temperature 12-60 hours is cooled down 50 DEG C with 1-3 DEG C/day of rate, then is down to 25 DEG C with the rate of 1-10 DEG C/h, opens container, i.e., Obtain Centimeter Level Be2(BO3) F nonlinear optical crystals.
Fluxing agent LiF-B in high temperature solution method in step c2O3、NaF-B2O3、KF-B2O3LiF and B in system2O3Rub You are than being 1-3:1-5, NaF and B2O3Molar ratio be 1-3:1-5；KF and B2O3Molar ratio be 1-3:1-5.
The fluoboric acid beryllium nonlinear optical crystal is preparing Nd:The fundamental frequency light for the 1064nm that YAG laser is exported into Purposes in 2 frequency multiplication of row, 3 frequencys multiplication, 4 frequencys multiplication, the harmonic wave light output of 5 frequencys multiplication or 6 frequencys multiplication.
Purposes of the fluoboric acid beryllium nonlinear optical crystal in preparing the deep ultraviolet frequency multiplication light output for generating 200nm.
The fluoboric acid beryllium nonlinear optical crystal is preparing times frequency generator, upper frequency converter, lower frequency converter Or the purposes in optical parametric oscillator.
Fluoboric acid beryllium compound of the present invention, chemical formula Be2(BO3) F, using hydro-thermal method or solid reaction process Fluoboric acid beryllium compound is prepared by following chemical equation：
(1)2BeO+NH4F+H3BO3→Be2(BO3)F+2H2O+NH3
(2)4BeO+2HF+B2O3→2Be2(BO3)F+H2O
(3)8BeO+2HBF4+H2O+B2O3→4Be2(BO3)F+4HF
(4)4BeO+2NH4F+B2O3→2Be2(BO3)F+H2O+2NH3
(5)2Be(OH)2+NH4F+H3BO3→Be2(BO3)F+4H2O+NH3
(6)4Be(OH)2+2HF+B2O3→2Be2(BO3)F+5H2O
(7)8Be(OH)2+2HBF4+B2O3→4Be2(BO3)F+4HF+7H2O
(8)4Be(OH)2+2NH4F+B2O3→2Be2(BO3)F+5H2O+2NH3
(9)2Be(NO3)2+NH4F+H3BO3→Be2(BO3)F+2H2O+4NO2+NH3
(10)4Be(NO3)2+2HF+B2O3→2Be2(BO3)F+H2O+8NO2
(11)8Be(NO3)2+2HBF4+9H2O+B2O3→4Be2(BO3)F+4HF+16HNO3
(12)4Be(NO3)2+2NH4F+B2O3→2Be2(BO3)F+H2O+8NO2+2NH3
(13)2BeCO3+NH4F+H3BO3→Be2(BO3)F+2H2O+2CO2+NH3
(14)4BeCO3+2HF+B2O3→2Be2(BO3)F+H2O+4CO2
(15)8BeCO3+2HBF4+H2O+B2O3→4Be2(BO3)F+4HF+8CO2
(16)4BeCO3+2NH4F+B2O3→2Be2(BO3)F+H2O+4CO2+2NH3
The molecular formula of fluoboric acid beryllium nonlinear optical crystal of the present invention, the crystal is Be2(BO3) F, space groupObtained crystal has wider transmission region, still has higher transmitance, transmission region purple in 200nm-7 μ ms The outer cut-off side that penetrates is 138nm, and the infrared cut-off side that penetrates is 8.5 μm, and nonlinear optical effect is about 1.8 times of KDP, this crystal Prepare simple, growth cycle is short, easy to process and preserve, and has many advantages, such as easy to operate, is easy to get large-size crystals.Using Device for non-linear optical uses Nd at room temperature made of the fluoboric acid beryllium nonlinear optical crystal that the method for the invention obtains: YAG Q-switched lasers make light source, and incident wavelength is the infrared light of 1064nm, and output wavelength is the green laser of 532nm, and laser is strong Degree is equivalent to 1.8 times of KDP.
The fluoboric acid beryllium nonlinear optical crystal is to optical manufacturing precision without particular/special requirement.
Description of the drawings
Fig. 1 is the powder x-ray diffraction collection of illustrative plates of the present invention；
Fig. 2 is the crystal structure figure of the present invention；
Fig. 3 is the fundamental diagram for the device for non-linear optical that the present invention makes, and is laser including (1), (2) are Convex lens, (3) are fluoboric acid beryllium nonlinear optical crystal, and (4) are Amici prism, and (5) are filter plate, and ω is the frequency for reflecting light Rate is equal to 2 times of incident light frequency or incident light frequency.
Specific implementation mode
Below in conjunction with drawings and examples, the present invention is described in detail：
Embodiment 1
With chemical equation 8BeO+2HBF4+H2O+B2O3→4Be2(BO3) for F+4HF, Be is synthesized using hydro-thermal method2 (BO3) F compounds, it specifically grasps and follows these steps to carry out：
By BeO, HBF4And B2O3Molar ratio be 8:2:1, BeO is dissolved in HBF4In, B is then added2O3, will be incomplete The mixture of dissolving temperature be 30 DEG C at ultrasonic wave in handle 1 hour, so that it is sufficiently mixed dissolving；Then it is loaded into dry Only, in polytetrafluoroethyllining lining of the free of contamination volume for the water heating kettle of 25mL, and by water heating kettle screwing hermetic, it is placed on drying In case, 210 DEG C are warming up to the rate of 25 DEG C/h of temperature, then constant temperature 3 days is down to 25 DEG C with the rate of 10 DEG C/h, open water Hot kettle is to get to compound Be2(BO3)F。
Embodiment 2
With chemical equation 2Be (OH)2+NH4F+H3BO3→Be2(BO3)F+4H2O+NH3For, it is closed using solid reaction process At Be2(BO3) F compounds, it specifically grasps and follows these steps to carry out：
By Be (OH)2、NH4F and H3BO3In molar ratio 2:1:1 ratio is uniformly mixed, and is fitted into quartz ampoule and is sealed, is put into In resistance furnace, 500 DEG C are warming up to the rate of 15 DEG C/h of temperature, then constant temperature 12 hours is down to 25 DEG C with the rate of 10 DEG C/h, Obtain compound Be2(BO3)F。
Embodiment 3
With chemical equation 4BeO+2HF+B2O3→2Be2(BO3)F+H2For O, Be is prepared using hydro-thermal method2(BO3) F crystalline substances Body, specific behaviour follow these steps to carry out：
A, BeO, HF and B are pressed2O3Molar ratio be 4:2:1, BeO is dissolved in HF, B is then added2O3, will be incomplete The mixture of dissolving temperature be 40 DEG C at ultrasonic wave in handle 1 hour, so that it is sufficiently mixed dissolving；
B, the obtained mixtures of step a are transferred to poly- the four of clean, the free of contamination autoclave that volume is 25mL In vinyl fluoride liner, and by reaction kettle screwing hermetic；
C, autoclave is placed in insulating box, 200 DEG C is warming up to by the rate of 20 DEG C/h, constant temperature 3 days, then with 10 The rate of temperature fall of DEG C/day is down to room temperature；Autoclave is opened, that is, obtains Be2(BO3) F compounds and seed crystal；
D, the Be for obtaining step c2(BO3) F seed crystals be put into volume be 25mL stainless steel autoclave platinum liner In, the Be that step c is obtained is added2(BO3) F compounds, 5mL deionized waters are then added, and by reaction kettle screwing hermetic, it will be high Pressure reaction kettle is placed in Muffle furnace, and 300 DEG C are warming up to by the rate of 30 DEG C/h, constant temperature 8 days, then fast with the cooling of 20 DEG C/day Rate is down to room temperature, opens autoclave, that is, obtains the Be that size is 5mm × 5mm × 3mm2(BO3) F nonlinear optical crystals.
Embodiment 4
With chemical equation 4Be (NO3)2+2HF+B2O3→2Be2(BO3)F+H2O+8NO2For, it is prepared using hydro-thermal method Be2(BO3) F crystal, it specifically grasps and follows these steps to carry out：
A, Be (NO are pressed3)2, HF and B2O3Molar ratio be 2:1:1, by Be (NO3)2It is dissolved in HF, B is then added2O3, It is handled 1 hour in ultrasonic wave at being 60 DEG C in temperature by the mixture of endless fully dissolved, it is made to be sufficiently mixed dissolving；
B, the obtained mixtures of step a are transferred to poly- the four of clean, the free of contamination autoclave that volume is 100mL In vinyl fluoride liner, and by reaction kettle screwing hermetic；
C, autoclave is placed in insulating box, 230 DEG C is warming up to by the rate of 60 DEG C/h, constant temperature 10 days, then with The rate of temperature fall of 100 DEG C/day is down to room temperature；Autoclave is opened, that is, obtains Be2(BO3) F compounds and seed crystal；
D, the Be for obtaining step c2(BO3) F seed crystals be put into volume be 100mL stainless steel autoclave platinum in In lining, the Be that step c is obtained is added2(BO3) F compounds, 15mL deionized waters are then added, and by reaction kettle screwing hermetic, it will Autoclave is placed in Muffle furnace, and 500 DEG C are warming up to by the rate of 60 DEG C/h, constant temperature 15 days, then with the drop of 100 DEG C/day Warm rate is down to room temperature；Autoclave is opened, that is, obtains the Be that size is 6mm × 5mm × 4mm2(BO3) F non-linear optical crystals Body.
Embodiment 5
With chemical equation 8BeCO3+2HBF4+H2O+B2O3→4Be2(BO3)F+4HF+8CO2For, using hydro-thermal legal system Standby Be2(BO3) F crystal, it specifically grasps and follows these steps to carry out：
A, BeCO is pressed3、HBF4And B2O3Molar ratio be 8:1:4, by BeCO3It is dissolved in HBF4In, B is then added2O3, will The mixture of endless fully dissolved temperature be 45 DEG C at ultrasonic wave in handle 1 hour, so that it is sufficiently mixed dissolving；
B, the obtained mixtures of step a are transferred to poly- the four of clean, the free of contamination autoclave that volume is 50mL In vinyl fluoride liner, and by reaction kettle screwing hermetic；
Autoclave is placed in insulating box by c, and 150 DEG C are warming up to by the rate of 40 DEG C/h, constant temperature 15 days, then with 80 The rate of temperature fall of DEG C/day is down to room temperature, opens autoclave, that is, obtains Be2(BO3) F compounds and seed crystal；
D, the Be for obtaining step c2(BO3) F seed crystals be put into volume be 50mL stainless steel autoclave platinum liner In, the Be that step c is obtained is added2(BO3) F compounds, 10mL deionized waters are then added, and by reaction kettle screwing hermetic, it will be high Pressure reaction kettle is placed in Muffle furnace, and 350 DEG C are warming up to by the rate of 20 DEG C/h, constant temperature 10 days, then fast with the cooling of 70 DEG C/day Rate is down to room temperature, opens autoclave, that is, obtains the Be that size is 7mm × 5mm × 3mm2(BO3) F nonlinear optical crystals.
Embodiment 6
With chemical equation 8BeO+2HBF4+H2O+B2O3→4Be2(BO3) for F+4HF, Be is prepared using hydro-thermal method2 (BO3) F crystal, it specifically grasps and follows these steps to carry out：
A, BeO, HBF are pressed4And B2O3Molar ratio be 6:2:1, BeO is dissolved in HBF4In, B is then added2O3, will be endless The mixture of fully dissolved temperature be 35 DEG C at ultrasonic wave in handle 1 hour, so that it is sufficiently mixed dissolving；
B, the obtained mixtures of step a are transferred to poly- the four of clean, the free of contamination autoclave that volume is 30mL In vinyl fluoride liner, and by reaction kettle screwing hermetic；
C, autoclave is placed in insulating box, 180 DEG C is warming up to by the rate of 30 DEG C/h, constant temperature 9 days, then with 60 The rate of temperature fall of DEG C/day is down to room temperature, opens autoclave, that is, obtains Be2(BO3) F compounds and seed crystal；
D, the Be for obtaining step c2(BO3) F seed crystals be put into volume be 40mL stainless steel autoclave platinum liner In, the Be that step c is obtained is added2(BO3) F compounds, 8mL deionized waters are then added, and by reaction kettle screwing hermetic, it will be high Pressure reaction kettle is placed in Muffle furnace, and 300 DEG C are warming up to by the rate of 25 DEG C/h, constant temperature 5 days, then fast with the cooling of 55 DEG C/day Rate is down to room temperature, opens autoclave, that is, obtains the Be that size is 5mm × 4mm × 2mm2(BO3) F nonlinear optical crystals.
Embodiment 7
With chemical equation 4Be (OH)2+2HF+B2O3→2Be2(BO3)F+5H2For O, Be is prepared using hydro-thermal method2 (BO3) F crystal, it specifically grasps and follows these steps to carry out：
A, Be (OH) is pressed2, HF and B2O3Molar ratio be 1:4:2, by Be (OH)2It is dissolved in HF, B is then added2O3, will The mixture of endless fully dissolved temperature be 55 DEG C at ultrasonic wave in handle 1 hour, so that it is sufficiently mixed dissolving；
B, the obtained mixtures of step a are transferred to poly- the four of clean, the free of contamination autoclave that volume is 40mL In vinyl fluoride liner, and by reaction kettle screwing hermetic；
C, autoclave is placed in insulating box, 210 DEG C is warming up to by the rate of 40 DEG C/h, constant temperature 6 days, then with 90 The rate of temperature fall of DEG C/day is down to room temperature, opens autoclave, that is, obtains Be2(BO3) F compounds and seed crystal；
D, the Be for obtaining step c2(BO3) F seed crystals be put into volume be 70mL stainless steel autoclave platinum liner In, the Be that step c is obtained is added2(BO3) F compounds, 2mL deionized waters are then added, and by reaction kettle screwing hermetic, it will be high Pressure reaction kettle is placed in Muffle furnace, and 480 DEG C are warming up to by the rate of 35 DEG C/h, constant temperature 7 days, then fast with the cooling of 45 DEG C/day Rate is down to room temperature, opens autoclave, that is, obtains the Be that size is 7mm × 8mm × 4mm2(BO3) F nonlinear optical crystals.
Embodiment 8
With chemical equation 4BeCO3+2HF+B2O3→2Be2(BO3)F+H2O+4CO2For, Be is prepared using hydro-thermal method2 (BO3) F crystal, it specifically grasps and follows these steps to carry out：
A, BeCO is pressed3, HF and B2O3Molar ratio be 8:8:1, by BeCO3It is dissolved in HF, B is then added2O3, will be endless The mixture of fully dissolved temperature be 25 DEG C at ultrasonic wave in handle 1 hour, so that it is sufficiently mixed dissolving；
B, the obtained mixtures of step a are transferred to poly- the four of clean, the free of contamination autoclave that volume is 85mL In vinyl fluoride liner, and by reaction kettle screwing hermetic；
C, autoclave is placed in insulating box, 220 DEG C is warming up to by the rate of 50 DEG C/h, constant temperature 10 days, then with The rate of temperature fall of 80 DEG C/day is down to room temperature, opens autoclave, that is, obtains Be2(BO3) F compounds and seed crystal；
D, the Be for obtaining step c2(BO3) F seed crystals be put into volume be 60mL stainless steel autoclave platinum liner In, the Be that step c is obtained is added2(BO3) F compounds, 5mL deionized waters are then added, and by reaction kettle screwing hermetic, it will be high Pressure reaction kettle is placed in Muffle furnace, and 380 DEG C are warming up to by the rate of 55 DEG C/h, constant temperature 9 days, then fast with the cooling of 100 DEG C/day Rate is down to room temperature, opens autoclave, that is, obtains the Be that size is 6mm × 7mm × 3mm2(BO3) F nonlinear optical crystals.
Embodiment 9
With chemical equation 8Be (NO3)2+2HBF4+9H2O+B2O3→4Be2(BO3)F+4HF+16HNO3For, using water Hot method prepares Be2(BO3) F crystal, it specifically grasps and follows these steps to carry out：
A, Be (NO are pressed3)2、HBF4And B2O3Molar ratio be 2:7:1, by Be (NO3)2It is dissolved in HBF4In, then it is added B2O3, by the mixture of endless fully dissolved temperature be 40 DEG C at ultrasonic wave in handle 1 hour, so that it is sufficiently mixed dissolving；
B, the obtained mixtures of step a are transferred to poly- the four of clean, the free of contamination autoclave that volume is 65mL In vinyl fluoride liner, and by reaction kettle screwing hermetic；
C, autoclave is placed in insulating box, 160 DEG C is warming up to by the rate of 30 DEG C/h, constant temperature 4 days, then with 60 The rate of temperature fall of DEG C/day is down to room temperature, opens autoclave, that is, obtains Be2(BO3) F compounds and seed crystal；
D, the Be for obtaining step c2(BO3) F seed crystals be put into volume be 60mL stainless steel autoclave platinum liner In, the Be that step c is obtained is added2(BO3) F compounds, 12mL deionized waters are then added, and by reaction kettle screwing hermetic, it will be high Pressure reaction kettle is placed in Muffle furnace, and 400 DEG C are warming up to by the rate of 25 DEG C/h, constant temperature 15 days, then fast with the cooling of 50 DEG C/day Rate is down to room temperature, opens autoclave, that is, obtains the Be of size 9mm × 7mm × 2mm2(BO3) F nonlinear optical crystals.
Embodiment 10
With chemical equation 8Be (OH)2+2HBF4+B2O3→4Be2(BO3)F+4HF+7H2For O, prepared using hydro-thermal method Be2(BO3) F crystal, it specifically grasps and follows these steps to carry out：
A, Be (NO are pressed3)2、HBF4And B2O3Molar ratio be 2:7:1, by Be (NO3)2It is dissolved in HBF4In, then it is added B2O3, by the mixture of endless fully dissolved temperature be 40 DEG C at ultrasonic wave in handle 1 hour, so that it is sufficiently mixed dissolving；
B, the obtained mixtures of step a are transferred to poly- the four of clean, the free of contamination autoclave that volume is 65mL In vinyl fluoride liner, and by reaction kettle screwing hermetic；
C, autoclave is placed in insulating box, 160 DEG C is warming up to by the rate of 30 DEG C/h, constant temperature 4 days, then with 60 The rate of temperature fall of DEG C/day is down to room temperature, opens autoclave, that is, obtains Be2(BO3) F compounds and seed crystal；
D, the Be for obtaining step c2(BO3) F seed crystals be put into volume be 60mL stainless steel autoclave platinum liner In, the Be that step c is obtained is added2(BO3) F compounds, 12mL deionized waters are then added, and by reaction kettle screwing hermetic, it will be high Pressure reaction kettle is placed in Muffle furnace, and 400 DEG C are warming up to by the rate of 25 DEG C/h, constant temperature 15 days, then fast with the cooling of 50 DEG C/day Rate is down to room temperature, opens autoclave, that is, obtains the Be of size 1mm × 6mm × 15mm2(BO3) F nonlinear optical crystals.
Embodiment 11
With chemical equation 4BeO+2NH4F+B2O3→2Be2(BO3)F+H2O+2NH3For, it is prepared using high temperature solution method Be2(BO3) F crystal, it specifically grasps and follows these steps to carry out：
A, by BeO, NH4F and B2O3In molar ratio 4:2:1 is uniformly mixed, and is fitted into quartz ampoule and seals, is put into resistance furnace, 400 DEG C are warming up to the rate of 10 DEG C/h, then constant temperature 12 hours is down to 25 DEG C with the rate of 1 DEG C/h, open quartz ampoule, i.e., Obtain compound Be2(BO3)F；
B, the compound Be for obtaining step a2(BO3) F is fitted into the quartz ampoule of Φ 10mm, quartz ampoule is vacuumized, vacuum Degree reaches 1 × 10-3Pa is put into flame gun Vacuum Package in Muffle furnace, is warming up to 400 DEG C with the rate of 10 DEG C/h, constant temperature 12 Hour, 25 DEG C then are down to the rate of 1 DEG C/h, quartz ampoule is opened, obtains Be2(BO3) F seed crystals；
C, the Be for obtaining step b2(BO3) F seed crystals be placed on container be quartz ampoule bottom, the change for then obtaining step a Close object Be2(BO3) F and fluxing agent be LiF in molar ratio 1:1 mixing, is put into quartz ampoule, quartz ampoule is vacuumized, vacuum degree reaches To 1 × 10-3Pa, with flame gun Vacuum Package；
D, it by after the quartzy seal of tube in step c, is put into resistance furnace, is warming up to 400 DEG C with the rate of 20 DEG C/h, constant temperature 12 hours, cooled down 50 DEG C with the rate of 1 DEG C/day, then 25 DEG C are down to the rate of 1 DEG C/h, open quartz ampoule, that is, obtaining size is The Be of 6mm × 4mm × 2mm2(BO3) F nonlinear optical crystals.
Embodiment 12
With chemical equation 4Be (OH)2+2NH4F+B2O3→2Be2(BO3)F+5H2O+2NH3For, using high temperature solution method Prepare Be2(BO3) F crystal, it specifically grasps and follows these steps to carry out：
A, by Be (OH)2、NH4F and B2O3In molar ratio 8:1:3 are uniformly mixed, and are fitted into quartz ampoule and seal, are put into resistance In stove, 750 DEG C are warming up to the rate of 25 DEG C/h, then constant temperature 48 hours is down to 25 DEG C with the rate of 10 DEG C/h, open quartz Pipe is to get to compound Be2(BO3)F；
B, the compound Be for obtaining step a2(BO3) F is fitted into the quartz ampoule of Φ 10mm, quartz ampoule is vacuumized, vacuum Degree reaches 1 × 10-3Pa is put into flame gun Vacuum Package in Muffle furnace, is warming up to 750 DEG C with the rate of 25 DEG C/h, constant temperature 60 Hour, 25 DEG C then are down to the rate of 5 DEG C/h, quartz ampoule is opened, obtains Be2(BO3) F seed crystals；
C, the Be for obtaining step b2(BO3) F seed crystals be placed on container be quartz ampoule bottom, the change for then obtaining step a Close object Be2(BO3) F and fluxing agent be NaF in molar ratio 1:5 mixing, are put into quartz ampoule, quartz ampoule are vacuumized, vacuum degree reaches To 1 × 10-3Pa, with flame gun Vacuum Package；
D, it by after the quartzy seal of tube in step c, is put into resistance furnace, is warming up to 750 DEG C with the rate of 40 DEG C/h, constant temperature 60 hours, cooled down 50 DEG C with the rate of 3 DEG C/day, then 25 DEG C are down to the rate of 10 DEG C/h, opened quartz ampoule, that is, obtain size For the Be of 5mm × 8mm × 3mm2(BO3) F nonlinear optical crystals.
Embodiment 13
With chemical equation 2BeCO3+NH4F+H3BO3→Be2(BO3)F+2H2O+2CO2+NH3For, using high temperature solution Method prepares Be2(BO3) F crystal, it specifically grasps and follows these steps to carry out：
A, by BeCO3、NH4F and H3BO3In molar ratio 1:4:2 are uniformly mixed, and are fitted into quartz ampoule and seal, are put into resistance furnace In, 650 DEG C are warming up to the rate of 20 DEG C/h of temperature, then constant temperature 35 hours is down to 25 DEG C with the rate of 8 DEG C/h, open stone English pipe is to get to compound Be2(BO3)F；
B, the compound Be for obtaining step a2(BO3) F is fitted into the quartz ampoule of Φ 10mm, quartz ampoule is vacuumized, vacuum Degree reaches 1 × 10-3Pa is put into flame gun Vacuum Package in Muffle furnace, is warming up to 650 DEG C with the rate of 15 DEG C/h, constant temperature 50 Hour, 25 DEG C then are down to the rate of 3 DEG C/h, quartz ampoule is opened, obtains Be2(BO3) F seed crystals；
C, the Be for obtaining step b2(BO3) F seed crystals be placed on container be quartz ampoule bottom, the change for then obtaining step a Close object Be2(BO3) F and fluxing agent be KF in molar ratio 1:4 mixing, are put into quartz ampoule, quartz ampoule are vacuumized, vacuum degree reaches To 1 × 10-3Pa, with flame gun Vacuum Package；
D, it by after the quartzy seal of tube in step c, is put into resistance furnace, is warming up to 550 DEG C with the rate of 30 DEG C/h, constant temperature 30 hours, cooled down 50 DEG C with the rate of 2 DEG C/day, then 25 DEG C are down to the rate of 5 DEG C/h, opened quartz ampoule, that is, obtain large scale For the Be of 14mm × 7mm × 5mm2(BO3) F nonlinear optical crystals.
Embodiment 14
With chemical equation 2BeO+NH4F+H3BO3→Be2(BO3)F+2H2O+NH3For, it is prepared using high temperature solution method Be2(BO3) F crystal, it specifically grasps and follows these steps to carry out：
A, by BeO, NH4F and H3BO3In molar ratio 6:1:3 are uniformly mixed, and are fitted into quartz ampoule and seal, are put into resistance furnace In, 550 DEG C are warming up to the rate of 15 DEG C/h of temperature, then constant temperature 30 hours is down to 25 DEG C with the rate of 6 DEG C/h of temperature, is beaten Quartz ampoule is opened to get to compound Be2(BO3)F；
B, the compound Be for obtaining step a2(BO3) F is fitted into the quartz ampoule of Φ 10mm, quartz ampoule is vacuumized, vacuum Degree reaches 1 × 10-3Pa is put into flame gun Vacuum Package in Muffle furnace, is warming up to 450 DEG C with the rate of 12 DEG C/h, constant temperature 40 Hour, 25 DEG C then are down to the rate of 2 DEG C/h, quartz ampoule is opened, obtains Be2(BO3) F seed crystals；
C, the Be for obtaining step b2(BO3) F seed crystals be placed on container be quartz ampoule bottom, the change for then obtaining step a Close object Be2(BO3) F and fluxing agent be LiF-B2O3In molar ratio 1:3 mixing, are put into quartz ampoule, quartz ampoule are vacuumized, very Reciprocal of duty cycle reaches 1 × 10-3Pa, with flame gun Vacuum Package, wherein fluxing agent LiF and B2O3Molar ratio is 1:3；
D, it by after the quartzy seal of tube in step c, is put into resistance furnace, is warming up to 450 DEG C with the rate of 25 DEG C/h, constant temperature 32 hours, cooled down 50 DEG C with the rate of 1 DEG C/day, then 25 DEG C are down to the rate of 3 DEG C/h, open quartz ampoule, that is, obtaining size is The Be of 5mm × 4mm × 2mm2(BO3) F nonlinear optical crystals.
Embodiment 15
With chemical equation 4BeO+2NH4F+B2O3→2Be2(BO3)F+H2O+2NH3For, it is prepared using high temperature solution method Be2(BO3) F crystal, it specifically grasps and follows these steps to carry out：
A, by BeO, NH4F and B2O3In molar ratio 2:8:1 is uniformly mixed, and is fitted into quartz ampoule and seals, is put into resistance furnace, 600 DEG C are warming up to the rate of 12 DEG C/h, then constant temperature 20 hours is down to 25 DEG C with the rate of 4 DEG C/h, open quartz ampoule, i.e., Obtain compound Be2(BO3)F；
B, the compound Be for obtaining step a2(BO3) F is fitted into the quartz ampoule of Φ 10mm, quartz ampoule is vacuumized, vacuum Degree reaches 1 × 10-3Pa is put into flame gun Vacuum Package in Muffle furnace, is warming up to 600 DEG C with the rate of 15 DEG C/h, constant temperature 20 Hour, 25 DEG C then are down to the rate of 1 DEG C/h, quartz ampoule is opened, obtains Be2(BO3) F seed crystals；
C, the Be for obtaining step b2(BO3) F seed crystals be placed on container be quartz ampoule bottom, the change for then obtaining step a Close object Be2(BO3) F and fluxing agent be NaF-B2O3In molar ratio 1:4 mixing, are put into quartz ampoule, quartz ampoule are vacuumized, very Reciprocal of duty cycle reaches 1 × 10-3Pa, with flame gun Vacuum Package, wherein fluxing agent NaF and B2O3Molar ratio is 1:5；
D, it by after the quartzy seal of tube in step c, is put into resistance furnace, is warming up to 600 DEG C with the rate of 20 DEG C/h, constant temperature 20 hours, cooled down 50 DEG C with the rate of 2 DEG C/day, then 25 DEG C are down to the rate of 2 DEG C/h, open quartz ampoule, that is, obtaining size is The Be of 13mm × 2mm × 4mm2(BO3) F nonlinear optical crystals.
Embodiment 16
With chemical equation 2Be (NO3)2+NH4F+H3BO3→Be2(BO3)F+2H2O+4NO2+NH3For, using high temperature melting Liquid method prepares Be2(BO3) F crystal, it specifically grasps and follows these steps to carry out：
A, by Be (NO3)2、NH4F and H3BO3In molar ratio 2:1:4 are uniformly mixed, and are fitted into quartz ampoule and seal, are put into resistance In stove, 500 DEG C are warming up to the rate of 10 DEG C/h, then constant temperature 15 hours is down to 25 DEG C with the rate of 4 DEG C/h, open quartz Pipe is to get to compound Be2(BO3)F；
B, the compound Be for obtaining step a2(BO3) F is fitted into the quartz ampoule of Φ 10mm, quartz ampoule is vacuumized, vacuum Degree reaches 1 × 10-3Pa is put into flame gun Vacuum Package in Muffle furnace, is warming up to 520 DEG C with the rate of 10 DEG C/h, constant temperature 20 Hour, 25 DEG C then are down to the rate of 2 DEG C/h, quartz ampoule is opened, obtains Be2(BO3) F seed crystals；
C, the Be for obtaining step b2(BO3) F seed crystals be placed on container be quartz ampoule bottom, the change for then obtaining step a Close object Be2(BO3) F and fluxing agent be KF-B2O3In molar ratio 1:5 mixing, are put into quartz ampoule, quartz ampoule are vacuumized, vacuum Degree reaches 1 × 10-3Pa, with flame gun Vacuum Package, wherein fluxing agent KF and B2O3Molar ratio is 1:4；
D, it by after the quartzy seal of tube in step c, is put into resistance furnace, is warming up to 650 DEG C with the rate of 25 DEG C/h, constant temperature 24 hours, cooled down 50 DEG C with the rate of 3 DEG C/day, then 25 DEG C are down to the rate of 5 DEG C/h, open quartz ampoule, that is, obtaining size is The Be of 8mm × 9mm × 12mm2(BO3) F nonlinear optical crystals.
Embodiment 17
With chemical equation 4Be (NO3)2+2NH4F+B2O3→2Be2(BO3)F+H2O+8NO2+2NH3For, using high temperature Melt method prepares Be2(BO3) F crystal, it specifically grasps and follows these steps to carry out：
A, by Be (NO3)2、NH4F and H3BO3In molar ratio 7:3:2 are uniformly mixed, and are fitted into quartz ampoule and seal, are put into resistance In stove, 400 DEG C are warming up to the rate of 15 DEG C/h, then constant temperature 25 hours is down to 25 DEG C with the rate of 8 DEG C/h, open quartz Pipe is to get to compound Be2(BO3)F；
B, the compound Be for obtaining step a2(BO3) F is fitted into the quartz ampoule of Φ 10mm, quartz ampoule is vacuumized, vacuum Degree reaches 1 × 10-3Pa is put into flame gun Vacuum Package in Muffle furnace, is warming up to 720 DEG C with the rate of 18 DEG C/h, constant temperature 28 Hour, 25 DEG C then are down to the rate of 4 DEG C/h, quartz ampoule is opened, obtains Be2(BO3) F seed crystals；
C, the Be for obtaining step b2(BO3) F seed crystals be placed on container be quartz ampoule bottom, the change for then obtaining step a Close object Be2(BO3) F and fluxing agent be H3BO3In molar ratio 1:1 mixing, is put into quartz ampoule, quartz ampoule is vacuumized, vacuum degree Reach 1 × 10-3Pa, with flame gun Vacuum Package；
D, it by after the quartzy seal of tube in step c, is put into resistance furnace, is warming up to 700 DEG C with the rate of 35 DEG C/h, constant temperature 48 hours, cooled down 50 DEG C with the rate of 2 DEG C/day, then 25 DEG C are down to the rate of 8 DEG C/h, open quartz ampoule, that is, obtaining size is The Be of 7mm × 2mm × 16mm2(BO3) F nonlinear optical crystals.
Embodiment 18
With chemical equation 4BeCO3+2NH4F+B2O3→2Be2(BO3)F+H2O+4CO2+2NH3For, using high temperature solution Method prepares Be2(BO3) F crystal, it specifically grasps and follows these steps to carry out：
A, by BeCO3、NH4F and B2O3In molar ratio 2:7:4 are uniformly mixed, and are fitted into quartz ampoule and seal, are put into resistance furnace In, 500 DEG C are warming up to the rate of 20 DEG C/h, then constant temperature 45 hours is down to 25 DEG C with the rate of 4 DEG C/h, open quartz ampoule, Obtain compound Be2(BO3)F；
B, the compound Be for obtaining step a2(BO3) F is fitted into the quartz ampoule of Φ 10mm, quartz ampoule is vacuumized, vacuum Degree reaches 1 × 10-3Pa is put into flame gun Vacuum Package in Muffle furnace, is warming up to 590 DEG C with the rate of 20 DEG C/h, constant temperature 36 Hour, 25 DEG C then are down to the rate of 3 DEG C/h, quartz ampoule is opened, obtains Be2(BO3) F seed crystals；
C, the Be for obtaining step b2(BO3) F seed crystals be placed on container be quartz ampoule bottom, the change for then obtaining step a Close object Be2(BO3) F and fluxing agent be B2O3In molar ratio 1:2 mixing, are put into quartz ampoule, quartz ampoule are vacuumized, vacuum degree Reach 1 × 10-3Pa, with flame gun Vacuum Package；
D, it by after the quartzy seal of tube in step c, is put into resistance furnace, is warming up to 690 DEG C with the rate of 40 DEG C/h, constant temperature 54 hours, cooled down 50 DEG C with the rate of 1 DEG C/day, then 25 DEG C are down to the rate of 6 DEG C/h, open quartz ampoule, that is, obtaining size is The Be of 8mm × 8mm × 12mm2(BO3) F nonlinear optical crystals.
Embodiment 19
By any one Be of gained in embodiment 1-182(BO3) F nonlinear optical crystals, it is placed in 3 by shown in attached drawing 3 Position on, at room temperature, with adjust Q Nd:Light source is made in the 1064nm outputs of YAG laser, observes apparent 532nm frequencys multiplication Green light exports, and output intensity is about 1/5 times of equal conditions KDP.
Fig. 3 is shown, by adjusting Q Nd:YAG laser 1 sends out the infrared beam that wavelength is 1064nm and is penetrated through convex lens 2 Enter fluoboric acid beryllium nonlinear optical crystal, generation wavelength is the green frequency doubled light of 532nm, and outgoing beam 4 is containing wavelength The infrared light of 1064nm and the green light of 532nm obtain the frequency doubled light that wavelength is 532nm after filtered 5 elimination.

Claims (7)

1. a kind of compound fluoboric acid beryllium, it is characterised in that the chemical formula of the compound is Be2(BO3) F, molecular weight 95.83, Compound is synthesized using hydro-thermal method or solid reaction process.
2. a kind of fluoboric acid beryllium nonlinear optical crystal, it is characterised in that the chemical formula of the crystal is Be2(BO3) F, molecular weight is 95.83, do not have symmetrical centre, belongs to hexagonal crystal system, space group isCell parameter is α=β=90 °, γ=120 °, Z=2,
3. the preparation method of fluoboric acid beryllium nonlinear optical crystal according to claim 2, it is characterised in that use hydro-thermal Method synthesizes compound and growth crystal or solid reaction process synthesis compound and high temperature solution method grows crystal, and concrete operations are pressed The following steps carry out：
The hydro-thermal method synthesis compound and growth crystal：
A, Be in molar ratio:F:B=1-4:0.5-4:0.5-2 will contain Be compounds BeO, Be (OH)2、Be(NO3)2Or BeCO3It is molten Solution is in HF or HBF4In, B is then added2O3, by the mixture of endless fully dissolved temperature be 30-60 DEG C at ultrasonic wave in Reason 1 hour, makes it be sufficiently mixed dissolving；
B, solution in step a is transferred to the polytetrafluoroethyl-ne for clean, the free of contamination autoclave that volume is 25-100mL In alkene liner, and by reaction kettle screwing hermetic；
C, the autoclave in step b is placed in insulating box, is warming up to 150-230 DEG C by the rate of 20-60 DEG C/h, perseverance Warm 3-15 days, then room temperature is down to 10-100 DEG C/day of rate of temperature fall, autoclave is opened, that is, obtains Be2(BO3) F chemical combination Object and seed crystal；
D, the Be that will be obtained in step c2(BO3) F seed crystals be put into volume be 25-100mL stainless steel autoclave platinum in In lining, the Be obtained in step c is added2(BO3) F compounds, 1-15mL deionized waters are then added, and reaction kettle screwed close Envelope, autoclave is placed in Muffle furnace, and 250-500 DEG C is warming up to by the rate of 20-60 DEG C/h, constant temperature 3-15 days, then It is down to room temperature with 10-100 DEG C/day of rate of temperature fall, opens autoclave, that is, obtains Centimeter Level Be2(BO3) F nonlinear opticses Crystal；
The solid reaction process synthesis compound and high temperature solution method grow crystal：
A, Be compounds BeO, Be (OH) will be contained2、Be(NO3)2Or BeCO3, boride alloy H3BO3And B2O3, compound containing F is NH4F Be in molar ratio:F:B=1-4:0.5-4:0.5-2 is uniformly mixed, and is fitted into quartz ampoule and is sealed, is put into resistance furnace, with The rate of 10-25 DEG C/h is warming up to 400-750 DEG C, then constant temperature 12-48 hours is down to 25 DEG C, i.e., with the rate of 1-10 DEG C/h Obtain compound Be2(BO3)F；
B, the compound Be for obtaining step a2(BO3) F is fitted into the quartz ampoule of Φ 10mm, quartz ampoule is vacuumized, vacuum degree reaches To 1 × 10-3Pa is put into flame gun Vacuum Package in Muffle furnace, is warming up to 400-750 DEG C with the rate of 10-25 DEG C/h, perseverance It is 12-60 hours warm, 25 DEG C then are down to the rate of 1-5 DEG C/h, quartz ampoule is opened, obtains Be2(BO3) F seed crystal；
C, the Be for obtaining step b2(BO3) F seed crystals are placed on the bottom of clean, free of contamination quartz ampoule, then step a is obtained Compound Be2(BO3) F and fluxing agent be LiF, NaF, KF, LiF-B2O3、NaF-B2O3、KF-B2O3、H3BO3Or B2O3By mole Than 1:1-5 is mixed, and is put into quartz ampoule, quartz ampoule is vacuumized, vacuum degree reaches 1 × 10-3Pa, with flame gun Vacuum Package；
D, the container in step c is sealed, is put into resistance furnace, is warming up to 400-750 DEG C with the rate of 20-40 DEG C/h, constant temperature 12-60 hours, cooled down 50 DEG C with 1-3 DEG C/day of rate, then 25 DEG C are down to the rate of 1-10 DEG C/h, opened container, that is, obtain Centimeter Level Be2(BO3) F nonlinear optical crystals.
4. the preparation method of fluoboric acid beryllium nonlinear optical crystal according to claim 3, it is characterised in that high temperature solution method Fluxing agent LiF-B in step c2O3、NaF-B2O3、KF-B2O3LiF and B in system2O3Molar ratio be 1-3:1-5, NaF with B2O3Molar ratio be 1-3:1-5；KF and B2O3Molar ratio be 1-3:1-5.
5. fluoboric acid beryllium nonlinear optical crystal according to claim 2 is preparing Nd:What YAG laser was exported The fundamental frequency light of 1064nm carries out the purposes in the harmonic wave light output of 2 frequencys multiplication, 3 frequencys multiplication, 4 frequencys multiplication, 5 frequencys multiplication or 6 frequencys multiplication.
6. fluoboric acid beryllium nonlinear optical crystal according to claim 2 generates the deep ultraviolet frequency doubled light of 200nm preparing Purposes in output.
7. fluoboric acid beryllium nonlinear optical crystal according to claim 2 prepare times frequency generator, upper frequency converter, Purposes in lower frequency converter or optical parametric oscillator.
CN201810239405.9A 2018-03-22 2018-03-22 Compound fluoboric acid beryllium and fluoboric acid beryllium nonlinear optical crystal and its preparation method and application Pending CN108373158A (en)

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CN105624780A (en) * 2015-09-29 2016-06-01 中国科学院福建物质结构研究所 Nonlinear beryllium borate fluoride (BBF) optical crystal as well as preparation method and application thereof

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CN105624780A (en) * 2015-09-29 2016-06-01 中国科学院福建物质结构研究所 Nonlinear beryllium borate fluoride (BBF) optical crystal as well as preparation method and application thereof

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夏文兵等: "一种潜在的新型非线性光学材料——氟硼酸铍", 《人工晶体学报》 *

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Application publication date: 20180807